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61.
Jo E Sanna MG Gonzalez-Cabrera PJ Thangada S Tigyi G Osborne DA Hla T Parrill AL Rosen H 《Chemistry & biology》2005,12(6):703-715
The essential role of the sphingosine 1-phosphate (S1P) receptor S1P(1) in regulating lymphocyte trafficking was demonstrated with the S1P(1)-selective nanomolar agonist, SEW2871. Despite its lack of charged headgroup, the tetraaromatic compound SEW2871 binds and activates S1P(1) through a combination of hydrophobic and ion-dipole interactions. Both S1P and SEW2871 activated ERK, Akt, and Rac signaling pathways and induced S1P(1) internalization and recycling, unlike FTY720-phosphate, which induces receptor degradation. Agonism with receptor recycling is sufficient for alteration of lymphocyte trafficking by S1P and SEW2871. S1P(1) modeling and mutagenesis studies revealed that residues binding the S1P headgroup are required for kinase activation by both S1P and SEW2871. Therefore, SEW2871 recapitulates the action of S1P in all the signaling pathways examined and overlaps in interactions with key headgroup binding receptor residues, presumably replacing salt-bridge interactions with ion-dipole interactions. 相似文献
62.
Cabaleiro-Lago C Garcia-Río L Hervés P Pérez-Juste J 《The journal of physical chemistry. B》2005,109(47):22614-22622
The solvolysis reactivity of benzoyl chlorides entails a high sensitivity on medium properties. A systematic study of the reaction of a series of these substrates, varying the electron-withdrawing character of the substituent, has been performed in nonionic microemulsions. The kinetic effects due to variation of microemulsion compositions can be assigned to modifications in system properties, to be precise, to modifications in interface properties. Microemulsion properties that are obtained from kinetic analysis of solvolysis show a good agreement with the characterization of the microemulsion that was made via 1H NMR and solvatochromic fluorescence probes. Benzoyl chlorides with electron-donating groups react through a dissociative mechanism, whereas electron-withdrawing groups favor an associative mechanism. A comparative analysis of reactivity between the different substrates at the interface shows a variation in the contributions of both reaction pathways, associative and dissociative, to the whole reaction mechanism. The confined media shift the point where the mechanism changes from an associative to a dissociative pathway, far away from the turning point in water. Furthermore, the change in mechanism can be modulated by modification of the microemulsion composition. 相似文献
63.
Bergquist Peter L. Te’o V. S. Junior Gibbs Moreland D. Cziferszky Angela C. E. De Faria Fabricia P. Azevedo Maristela O. Nevalainen K. M. Helena 《Applied biochemistry and biotechnology》2002,98(1-9):165-176
Cost-effective production of enzymes for industrial processes makes the appropriate selection of the host-vector expression
system critical. We have developed two systems for the bulk production of bleaching enzymes from thermophiles. Kluyveromyces lactis has been developed as a secretion host employing expression vectors based on the 2μ-like plasmid pKD1 of Kluyveromyces drosophilarium. Our second system involves the filamentous fungus Trichoderma reesei. Fusion and nonfusion vectors have been constructed using the strong cellobiohydrolase 1 (cbh1) promoter. The KEX2 protease cleavage site and a 6 × HIS-tag have been incorporated to facilitate both cleavage and purification
of the mature foreign proteins. 相似文献
64.
Catellani M Mealli C Motti E Paoli P Perez-Carreño E Pregosin PS 《Journal of the American Chemical Society》2002,124(16):4336-4346
A series of dichloro-bridged arylbicycloheptylpalladium complexes have been synthesized and characterized by means of NMR spectroscopy. The compound [(C16H19)PdCl]2*CH2Cl2 with ortho and para methyl substituents at the arene has been characterized by means of X-ray diffraction techniques. The C(ipso) atom of the arene lies almost at the fourth planar coordination site of the metal [Pd-C(ipso) = 2.22(1) A (average)], and due to the arene's tilting, the substituted C(ortho) atom is relatively close to the metal atom [2.54(1) A (average)]. The coordinated C(ipso)-C(ortho) linkage, in a seemingly dihapto coordination, is anti with respect to the CH2 bridge of the bicycloheptyl unit. Variable-temperature NMR experiments for the para-substituted dimer 9 reveal restricted rotation of the two aryl groups about the corresponding C-C(ipso) bonds (DeltaE < or =17 kcal x mol(-1)). DFT-B3LYP calculations have been carried out on the known and similar monomer (phenylbicycloheptenyl)Pd(PPh3)I (4) and its related substituted derivatives. The essential results are as follows: (i) The potential energy surface for twisting the phenyl ring away from the symmetric eta(1) coordination in 4 is very flat (DeltaE < or = 1 kcal x mol(-1)) whereas an Atoms in Molecules analysis excludes the existence of an actual Pd-C(ortho) bond in the seemingly eta2-type conformer. (ii) Complete rotation of the unsubstituted phenyl ring is not facile but feasible. A significant strain affects the transition-state structure featuring a Pd-HC(aryl) agostic-type bond. The calculated destabilization of 10.3 kcal x mol(-1), with respect to the ground state, can be compared to the experimental barrier of the dimer 9. (iii) Various methyl-substituted derivatives of 4 have been optimized, and their structural and energetic trends are discussed. An almost ideal eta1 coordination is shown by the anti conformer of the C(ortho)-substituted complex due steric effects. For all of the other cases, a slipped eta2 coordination may be described. As a general conclusion, the unsaturated metal center receives pi electron density of the arene mainly through its C(ipso) atom. The effect may be slightly improved if the C(ortho) atom also gets closer to the metal, but in no case, does the slipped eta2 coordination seem to be crucial for the stability of the system. 相似文献
65.
Barros N. Feijóo S. Simoni A. Critter S. A. M. Airoldi C. 《Journal of Thermal Analysis and Calorimetry》2000,63(2):577-588
The microcalorimetric method was used to calculate the metabolic enthalpy change per mol of glucose degraded by soil microorganisms,
ΔH
met. This parameter has been calculated by microcalorimetry for many organic, inorganic and biochemical reactions, but there
is only some information about its quantification for microbial growth reactions in soils. Values of ΔH
met were calculated for different soil samples collected in Galicia (Spain) and Campinas (Săo Paolo, Brazil). Exponential microbial
growth was stimulated in all soil samples by the addition of glucose and power-time curves were recorded. Results showed changes
in the values of ΔH
met calculated for all the soil samples, suggesting a dependence of this value with the microbial growth rate constant, with
the percentage of growth, with the initial number of microorganisms of soil samples, with the quantity of glucose added and
with the strain of bacteria growing in soil.
The interpretation of variations of ΔH
met provides important qualitative and quantitative information. It reports data that allow to interpret from a qualitative point
of view, the increase in biomass as a consequence of the degradation of the organic matter in soil, to understand changes
in the percentages of soil organic matter and to know if the microbial population growing in differential soil samples is
homogeneous. Therefore, to report that value would be very important in ecological studies, but beforehand, it is necessary
to solve some problems that can appear in the experiments done to make the quantification
.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
66.
An amperometric flow-injection method for the determination of antithyroid drugs such as 6-methyl-2-thiouracil (MTU) using a carbon fiber cylindrical microelectrode-based detector is reported. A home-made flow-cell specially adapted for working with cylindrical microelectrodes ranging between 4 and 10 mm in length was used for this purpose. Methanol containing 0.05 mol l(-1) tetrabutylammonium perchlorate as the supporting electrolyte was employed, and a potential of +1.6 V was selected for the amperometric detection of MTU. No cleaning or electrode surface regeneration of the fiber was necessary during the whole working day. A limit of detection of 2.6x10(-7) mol l(-1) (37 mug MTU l(-1)) was achieved. The method was applied to the determination of MTU in spiked feed samples (peas and corn flour), at the 142 mug g(-1) level. The procedure involved the extraction of the drug in methanol, a clean-up step using Florisil cartridges and the use of the standard additions method. Recoveries of 81+/-6 and 85+/-8% were obtained for peas and corn flour, respectively. 相似文献
67.
A new software-controlled volume-based system for sample introduction in process flow injection analysis was developed. By using a multi-syringe burette coupled with one or two additional commutation valves, the multi-commuted injection of precise sample volumes was accomplished. Characteristics and performance of the injection system were studied by injecting an indicator in a buffered carrier. Three configurations were implemented in order to achieve two different tasks: the single injection of a sample in a two- or three-channels manifold, and the dual injection into different streams. The two channel flow system using the single injection was applied to the determination of free acidity in diluted samples containing high levels of iron(III), by employing the single point titration methodology. The precipitation of ferric hydroxide was prevented using the ammonium and sodium salts of oxalate and acetate as buffer titrant. Methyl Red was employed as indicator. The procedure allows determination of acid concentration in solutions with a Fe(III)/H+ molar ratio up to 0.2. Samples with higher Fe(III)/H+ molar ratios were spiked with a known strong acid at dilution. The three-channel configuration was applied to the determination of ferric ions, using, as reagent, a merging mixture of sulfuric acid and potassium thiocyanate. The double injection system was implemented in series in a single (three-channel) manifold in such a way that a different injection volume and a changed reagent were used for each analyte. It was applied to the separated or sequential determination of free acidity and ferric ions. In this configuration, iron(III) was determined using 0.5-0.7% (w/v) sodium salicylate solution as reagent. The systems can operate at up to 100, 84 and 78 injections per hour, respectively. Determinations on synthetic and process samples compared well with the reference values and procedures. Recoveries of 95-102% with a maximum RSD value of 5.4% were found for acidity. The respective values obtained for iron determinations were 96-105% and 4.3%. 相似文献
68.
López-Alarcón C Squella JA Núñez-Vergara LJ Baez H Camargo C 《Rapid communications in mass spectrometry : RCM》2002,16(24):2229-2238
A gas chromatography/mass spectrometry (GC/MS) method for the qualitative and quantitative determination of the calcium-channel antagonists C-4-substituted 1,4-dihydropyridines, and their corresponding N-ethyl derivatives, is presented. Also, the electrochemical oxidation and the reactivity of the compounds with alkyl radicals derived from 2,2'-azobis-(2-amidinopropane) were monitored by GC/MS. Mass spectral fragmentation patterns for the C-4-substituted 1,4-dihydropy-ridine parent drugs were significantly different from those of their oxidation products, generated either by electrochemical oxidation or by reaction with alkyl radicals. However, for N-ethyl-1,4-dihydropyridine compounds it was not possible to detect the final products (pyridinium salts) using these experimental conditions. 相似文献
69.
Amidines can be prepared on a solid support by reducing polymer-bound amidoximes with SnCl2·2H2O. The method has proved to be straightforward and highly efficient. Amidoximes attached to the solid support are readily available by treating resin-bound nitriles with hydroxylamine. 相似文献
70.
M. Kabešová I. Vargová T. Šramko J. Gažo 《Journal of Thermal Analysis and Calorimetry》1978,13(1):65-70
The influence of the position of the CH3 group in picoline and lutidine ligands on the degree of chemical change of the NCS groups in coordination compounds of the type Cu(NCS)2L2 (whereL=2-, 3- and 4-picoline, and 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-lutidine) is dealt with. The most marked effect of the CH3 group is found to be exerted in position 4. This effect of the methyl group on the degree of chemical change points to the mutual influence of the ligands in coordination compounds of Cu(II).
Zusammenfassung Der Artikel befaßt sich mit dem Einfluß der Lage der CH3 Gruppe in Pikolinen und Lutidinen als Liganden auf den Grad der chemischen Änderungen der Gruppen NSC in Koordinationsverbindungen des Typs Cu(NCS)2L2 (L=2-, 3- und 4-Pikoline, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- und 3,5-Lutidine). Der ausgeprägteste Effekt der CH3 Gruppe wurde in der Position 4 beobachtet. Dieser Einfluß der Methylgruppe auf das Ausmaß der chemischen Änderungen deutet auch auf die gegenseitige Wirkung der Liganden in Koordinationsverbindungen von Cu(II).
Résumé L'article a trait à l'influence de la position du groupe CH2 dans les picolines et lutidines, en tant que ligands, sur le degré des changements chimiques des groupes SCN dans les composés de coordination du type Cu(SCN)2L2 (L=2-, 3 et 4-picoline, 2,3-, 2,4-,2,5-, 2,6-, 3,4- et 3,6-lutidine). L'effet le plus prononcé du groupe CH3 s'observe en position 4. Cette influence du groupe méthyle sur le degré des changements chimiques indique aussi l'influence mutuelle des ligands dans les composés de coordination du Cu(II).
- , , NCS Cu(NCS)2,L2, L=2-, 3- 4- , 2.3-, 2.4-, 2.5-, 2.6-, 3.4- 3.5-. , 4. Cu(II).相似文献